Manufacture of alkyl substituted aryl sulphates



Patented Feb. 20, 1940 UNIT'D STAT-ES MANUFACTURE OF ALKYL SUBSTITUTEDARYL SULPHA'EE s Joseph L. Richmond, Woodstown, NHL, assignor to E. I.du .Pont de Nemours & Company,

Wilmington, 'DeL, a

corporation of Delaware 10 Claims.

This invention relates to new chemical compounds; theirmethods ofmanufacture, and their technical uses, and more particularly .to'thepreparation 'and use of new and improved surface active agents.

This invention has an an object'the preparation of new chemicalcompoundspossessing surface active properties, which can'be used asdetergents', wetting agents, emulsifying agents, dye

J bath assistants; and textile assistants. A further object is toprepare these'new ccmpounds'by novel and easily conducted methods whichgive high yields of products of good quality. A'still further objectisto apply these new products in various technical relations whereinsurface active compounds are commonly employed. Other objects willappear hereinafter.

These objects are accomplished by the following invention whichrelates-to the production and .uses of alkyl substituted aryl sulphateswherein the alkyl group contains eight or more carbon atoms and thesulphate groupis directly attached to'a carbon atom in thearyl'nucleus.

The following examplesillustrat'e but 'do not 5 jlimit'the manner inwhich this invention may be carried out.

Example 1 To 20 grams of decyl phenol (prepared by alkylating phenolwithn-"decylalcohol in the presence-'of'zinc-chloride') in 100 cubiccentimeters of'anhydrous ethyl ether'were added, slowly, with stirring,at a temperature of 0-10" 0., a solution of 11 grams of chlorosulphonicacid in cubic centimeters of ethyl ether. After all the acid solutionhad been added, the sulphation mass was stirred 15 minutes and pouredinto a mixture of ice and excess 50% caustic soda solution. The etherwas evaporated ofi, and the aqueous solution then evaporated to drynesson a steam bath under reduced pressure. The solid residue was extractedwith methanol to remove the sulphate ester, the methanol solutiondiluted with water and extracted twice with petroleum ether. Theextracted solution was evaporated to dryness.

i Foe product was a White, Waxy solid soluble in water with foaming.

Example 2 To grams of pyridine cooled to 0 C., were added 10 grams ofchlorosulphonic acid, and the temperature allowed to rise to 20 C. Tothis mixture was added a solution of 20 grams of dodecyl phenol in 60grams of pyridine at room temperature. After the addition, the contentsof the flask were stirred minutes and then poured into ice water andneutralized With'a 10% caustic soda solution. The solution wasevaporated .to dryness, and the product purified .as in'Exarnple l. Theproduct was a solid soluble in water with foaming.

The compoundsdisclosed inthe precedingexaniples are salts of allzylphenyl sulphates and not salts of alkyl phenol sulphonic acids. This isshownzby the fact that the compcunds..,dis closed in the examples can behydrolyzed 'by strongac'id and thereby converted back to the .alkylphenol, which was the starting material.

The higher alkyl phenyl sulphates possess excellent surface activeproperties. They are wetting agents or detergents, depending upon thesize and-configuration of the alkyl group. By altering the nature of thesubstituent alkyl groups, the surface active properties can be changed.The :salts of the higher alkyl phenyl sulphates are stable solids. Theycan be prepared dry and do not decompose on-standing.

The alkyl phenols which it is preferred-teemploy in this invention areprepared-by allrylating a lower phenol with an aliphatic alcohol usingsulphuric acid, zinc chloride, or boron triiluoride as a catalyst. If anormal primary alcohol is used, the secondary alkyl phenol isformed, asthe reaction does not appear to be a simple splitting out of waterbetween the alcohol and phenol. Using dode-cyl alcohol and phenol, thereaction is believed "to go as \follows:

Oils

Any of the higher alkyl phenols disclosed in Bousquet application,Serial Number @635, filed February 2, 1935, may be used as intermediatesfor preparing higher alkyl aryl sulphates coming within the purview ofthe present invention.

Other higher alkyl phenols which may be sulphated according to thepresent invention include mono-alkyl phenols such ootyl phenol, cetylphenol, octadecyl phenol, oleyl phenol, (2-ethyl hexyl) phenol;poly-alkyl phenols such as dioctyl phenol, dodecyl cresol, cetyl cresol,trioctyl phenol; substituted alpha and beta naphthols such as decylnaphthol, dodecyl naphthol; and phenols containing cyclic side chainssuch as cyclehexyl-cyclohexyl phenol and tetrahydro-naphthyl phenol.

The higher alkyl aryl sulphates of the present invention may be preparedby treating any of the higher alkyl phenols disclosed in the precedingparagraphs by any one of the usual sulphating methods. The sulphatingagents which'I prefer to employ in this invention are chlorosulphonicacid in ethyl ether and sulphur trioxide in pyridine. While I prefer tosulphate using chlorosulphonic acid in ethyl ether and sulphur trioxidein pyridine, it is also possible to use pyridine and potassiumpyrosulphate, sulphur trioxide in dimethyl aniline, sulphuric acid inethyl ether, sulphur trioxide in ethyl ether, sulphur trioxide in liquidsulphur dioxide, amino sulphonic acid, chlorosulphonic acid in diethylaniline, or other well known methods of sulphation. The procedure orsulphation can also be varied so that a solution of the surface activeagent instead of a solid is obtained. In some cases, the former is thepreferable form for the product.

While I prefer to use sodium hydroxide to neutralize these sulphatedphenols, it is also possible to neutralize with other inorganic basessuch as lithium hydroxide, potassium hydroxide, sodium carbonate,ammonia, or with such organic bases as trimethyl amine, triethanolamine, tetramethyl ammonium hydroxide, or methyl glucamine. When in theclaims I mention an alkyl substituted aryl sulphate, I intend to refergenerically to the products of the present invention irrespective ofwhether or how the acidic hydrogen of the sulphate group may have beenneutralized.

The compounds disclosed in this application constitute a new class ofsurface active agents. They are useful as wetting agents, detergents,lime-soap dispersing agents, dye bath assistants, emulsifying agents,penetrating agents, as a component of printing pastes, as wetting andspreading agents in fungicide and insecticide preparations, and, ingeneral, they are useful wherever a compound with surface activeproperties is desired.

The above description and examples are intended to be illustrative onlyand not to limit the scope of the invention. Any departure therefromwhich conforms to the spirit of the invention is intended to be includedwithin the scope of the appended claims.

I claim:

1. An alkyl substituted aryl sulphate of the benzene and naphthaleneseries wherein an alkyl group contains at least eight carbon atoms andthe sulphate group is directly attached to a carbon atom in the arylnucleus.

2. An alkyl substituted aryl sulphate of the benzene and naphthaleneseries wherein an alkyl group contains at least eight carbon atoms andis derived from a normal primary aliphatic alcohol containing eight ormore carbon atoms and the sulphate group is directly attached to acarbon atom in the aryl nucleus.

3. An alkyl substituted aryl sulphate wherein an alkyl group containsfrom eight to eighteen carbon atoms and is derived from a normal primary aliphatic alcohol containing from eight to 3 eighteen carbon atoms,the aryl radical belongs to the benzene series, and the sulphate groupis directly attached to a carbon atom in the aryl nucleus.

4. An alkyl substituted phenyl sulphate wherein the alkyl group containsfrom eight to eighteen carbon atoms and is derived from a normal primaryaliphatic alcohol containing from eight to eighteen carbon atoms and thesulphate group is directly attached to a carbon atom in the phenylnucleus.

5. An alkali metal salt of an alkyl substituted phenyl sulphate whereinthe alkyl group contains from eight to eighteen carbon atoms and isderived from a normal primary aliphatic alcohol containing from eight toeighteen carbon atoms and the sulphate group is directly attached to acarbon atom in the phenyl nucleus.

6. A process of preparing an alkali metal salt of an alkyl substitutedphenyl sulphate as defined in claim 5 which comprises reacting asulphating agent with an alkyl phenol wherein the aikyl group containsfrom eight to eighteen carbon atoms and is derived from a normal primaryaliphatic alcohol containing from eight eighteen carbon atoms.

7. The sodium salt of decyl phenyl sulphate.

8. A process of preparing the sodium salt of decyl phenyl sulphate whichcomprises adding an ethyl ether solution of chlorosulphonic acid to anethyl ether solution of decyl phenol, stirring the reaction mixture, andneutralizing the sulphated decyl phenol with a caustic soda solution.

9. The sodium salt of dodecyl phenyl sulphate.

10. A process of preparing the sodium salt of dodecyl phenyl sulphatewhich comprises adding a pyridine solution of dodecyl phenol to apyridine solution of chlorosulphcnic acid, stirring the reactionmixture, and neutralizing the sulphated dodecyl phenol with a causticsoda solution.

JOSEPH L. RICHMOND.

